US9828296B2 - Lead-free piezoelectric ceramic composition, method for producing same, piezoelectric element using lead-free piezoelectric ceramic composition, ultrasonic processing machine, ultrasonic drive device, and sensing device - Google Patents

Lead-free piezoelectric ceramic composition, method for producing same, piezoelectric element using lead-free piezoelectric ceramic composition, ultrasonic processing machine, ultrasonic drive device, and sensing device Download PDF

Info

Publication number
US9828296B2
US9828296B2 US14/232,146 US201214232146A US9828296B2 US 9828296 B2 US9828296 B2 US 9828296B2 US 201214232146 A US201214232146 A US 201214232146A US 9828296 B2 US9828296 B2 US 9828296B2
Authority
US
United States
Prior art keywords
crystal phase
piezoelectric ceramic
ceramic composition
phase
lead
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active, expires
Application number
US14/232,146
Other languages
English (en)
Other versions
US20140139070A1 (en
Inventor
Masato Yamazaki
Takayuki Matsuoka
Kazuaki Kitamura
Hideto Yamada
Toshiaki Kurahashi
Katsuya Yamagiwa
Kazushige Ohbayashi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Niterra Co Ltd
Original Assignee
NGK Spark Plug Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by NGK Spark Plug Co Ltd filed Critical NGK Spark Plug Co Ltd
Assigned to NGK SPARK PLUG CO., LTD. reassignment NGK SPARK PLUG CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KITAMURA, KAZUAKI, KURAHASHI, TOSHIAKI, MATSUOKA, TAKAYUKI, OHBAYASHI, KAZUSHIGE, YAMADA, HIDETO, YAMAGIWA, KATSUYA, YAMAZAKI, MASATO
Publication of US20140139070A1 publication Critical patent/US20140139070A1/en
Application granted granted Critical
Publication of US9828296B2 publication Critical patent/US9828296B2/en
Assigned to NITERRA CO., LTD. reassignment NITERRA CO., LTD. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: NGK SPARK PLUG CO., LTD.
Active legal-status Critical Current
Adjusted expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B06—GENERATING OR TRANSMITTING MECHANICAL VIBRATIONS IN GENERAL
    • B06B—METHODS OR APPARATUS FOR GENERATING OR TRANSMITTING MECHANICAL VIBRATIONS OF INFRASONIC, SONIC, OR ULTRASONIC FREQUENCY, e.g. FOR PERFORMING MECHANICAL WORK IN GENERAL
    • B06B1/00—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency
    • B06B1/02—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy
    • B06B1/06—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy operating with piezoelectric effect or with electrostriction
    • B06B1/0607—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy operating with piezoelectric effect or with electrostriction using multiple elements
    • B06B1/0611—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy operating with piezoelectric effect or with electrostriction using multiple elements in a pile
    • B06B1/0618—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy operating with piezoelectric effect or with electrostriction using multiple elements in a pile of piezo- and non-piezoelectric elements, e.g. 'Tonpilz'
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/495—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62685—Treating the starting powders individually or as mixtures characterised by the order of addition of constituents or additives
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
    • G01L23/00—Devices or apparatus for measuring or indicating or recording rapid changes, such as oscillations, in the pressure of steam, gas, or liquid; Indicators for determining work or energy of steam, internal-combustion, or other fluid-pressure engines from the condition of the working fluid
    • G01L23/22—Devices or apparatus for measuring or indicating or recording rapid changes, such as oscillations, in the pressure of steam, gas, or liquid; Indicators for determining work or energy of steam, internal-combustion, or other fluid-pressure engines from the condition of the working fluid for detecting or indicating knocks in internal-combustion engines; Units comprising pressure-sensitive members combined with ignitors for firing internal-combustion engines
    • G01L23/221—Devices or apparatus for measuring or indicating or recording rapid changes, such as oscillations, in the pressure of steam, gas, or liquid; Indicators for determining work or energy of steam, internal-combustion, or other fluid-pressure engines from the condition of the working fluid for detecting or indicating knocks in internal-combustion engines; Units comprising pressure-sensitive members combined with ignitors for firing internal-combustion engines for detecting or indicating knocks in internal combustion engines
    • G01L23/222—Devices or apparatus for measuring or indicating or recording rapid changes, such as oscillations, in the pressure of steam, gas, or liquid; Indicators for determining work or energy of steam, internal-combustion, or other fluid-pressure engines from the condition of the working fluid for detecting or indicating knocks in internal-combustion engines; Units comprising pressure-sensitive members combined with ignitors for firing internal-combustion engines for detecting or indicating knocks in internal combustion engines using piezoelectric devices
    • H01L41/1873—
    • H01L41/43—
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/09—Forming piezoelectric or electrostrictive materials
    • H10N30/093—Forming inorganic materials
    • H10N30/097—Forming inorganic materials by sintering
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H10N30/853—Ceramic compositions
    • H10N30/8542—Alkali metal based oxides, e.g. lithium, sodium or potassium niobates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
    • C04B2235/3203—Lithium oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3213—Strontium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3215—Barium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • C04B2235/3234—Titanates, not containing zirconia
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
    • C04B2235/3267—MnO2
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3275—Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3279—Nickel oxides, nickalates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3289—Noble metal oxides
    • C04B2235/3291—Silver oxides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/76—Crystal structural characteristics, e.g. symmetry
    • C04B2235/768—Perovskite structure ABO3
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/79—Non-stoichiometric products, e.g. perovskites (ABO3) with an A/B-ratio other than 1
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase

Definitions

  • the present invention relates to lead-free piezoelectric ceramic compositions used for piezoelectric elements and the like, and to ultrasonic processing machines, ultrasonic drive devices, and sensing devices using piezoelectric elements.
  • compositions represented by composition formula ANbO 3 (A is an alkali metal), for example, potassium sodium niobate ((K,Na)NbO 3 ), have been proposed as the materials of such lead-free piezoceramics (referred to as “lead-free piezoelectric ceramic composition”).
  • ANbO 3 lead-free piezoelectric ceramic compositions themselves are problematic, because of poor sinterability and poor humidity resistance.
  • Patent Reference 1 discloses a method whereby copper (Cu), lithium (Li), tantalum (Ta), and the like are added to ANbO 3 lead-free piezoelectric ceramic compositions to improve sinterability, and eventually, piezoelectric characteristics.
  • the piezoelectric ceramic compositions described in Patent Reference 1 improve sinterability, the compositions are inferior to conventional lead-containing piezoelectric ceramic compositions from the standpoint of piezoelectric characteristics, and are insufficient for practical applications.
  • the piezoelectric ceramic compositions described in Patent Reference 2 have a relatively high piezoelectric constant. A problem, however, is that, since the phase transition point falls between ⁇ 50° C. to +150° C., the characteristics abruptly fluctuate in the vicinity of the phase transition point.
  • a lead-free piezoelectric ceramic composition mainly includes: a first crystal phase in which a plurality of crystal grains formed of an alkali niobate/tantalate perovskite oxide having piezoelectric characteristics is bound to each other in a deposited state; and a second crystal phase formed of a compound containing titanium (Ti) and filling spaces between the plurality of crystal grains of the first crystal phase.
  • a first crystal phase in which a plurality of crystal grains formed of an alkali niobate/tantalate perovskite oxide having piezoelectric characteristics is bound to each other in a deposited state
  • a second crystal phase formed of a compound containing titanium (Ti) and filling spaces between the plurality of crystal grains of the first crystal phase.
  • the second crystal phase is contained in a content of 2 to 10 mol %.
  • insulation characteristics and piezoelectric characteristics can be further improved.
  • the lead-free piezoelectric ceramic composition may further include at least one metal element selected from copper (Cu), iron (Fe), and zinc (Zn), which is contained by being localized more in the second crystal phase than in the first crystal phase
  • at least one metal element selected from copper (Cu), iron (Fe), and zinc (Zn)
  • the lead-free piezoelectric ceramic composition may further include at least one metal element selected from cobalt (Co), copper (Cu), iron (Fe), and zinc (Zn), which is contained by being localized more in the second crystal phase than in the first crystal phase.
  • Co cobalt
  • Cu copper
  • Fe iron
  • Zn zinc
  • the lead-free piezoelectric ceramic composition may further include at least one metal element selected from zirconium (Zr) and calcium (Ca), which is contained by being localized more in the first crystal phase than in the second crystal phase.
  • Zr zirconium
  • Ca calcium
  • the compound forming the second crystal phase may be an A-Ti—B—O composite compound (wherein the element A is an alkali metal, the element B is at least one of niobium (Nb) and tantalum (Ta), and each of the contents of the element A, the element B, and titanium (Ti) is not zero).
  • the lead-free piezoelectric ceramic composition according to this aspect the second crystal phase can easily be formed.
  • the element A may be potassium (K).
  • the second crystal phase can easily be formed.
  • the element B may be niobium (Nb).
  • the Curie temperature (Tc) can be made higher than when the element B is tantalum (Ta).
  • the compound forming the second crystal phase has a lower melting point than the alkali niobate/tantalate perovskite oxide forming the first crystal phase.
  • the second crystal phase can easily be formed between the crystal grains of the first crystal phase.
  • a lead-free piezoelectric ceramic composition according to another aspect of the present invention is produced by mixing, molding, and firing a crystal powder formed of an alkali niobate/tantalate perovskite oxide having piezoelectric characteristics and a crystal powder formed of a compound that contains titanium (Ti).
  • the lead-free piezoelectric ceramic composition according to this aspect it is possible to form the first crystal phase in which a plurality of crystal grains formed of an alkali niobate/tantalate perovskite oxide is bound to each other in a deposited state, and the second crystal phase formed of a compound that contains titanium (Ti) and filling the spaces between the crystal grains in the first crystal phase. In this way, the piezoelectric characteristics can be improved more than in other lead-free piezoelectric ceramic compositions that do not include the second crystal phase.
  • a piezoelectric element according to an aspect of the present invention includes a piezoceramic formed from the lead-free piezoelectric ceramic composition according to the above-described aspects; and an electrode mounted on the piezoceramic. With the piezoelectric element according to this aspect, piezoelectric characteristics can be improved.
  • An ultrasonic processing machine includes the piezoelectric element according to the above-described aspect. With the ultrasonic processing machine according to this aspect, process performance and heat durability can be improved.
  • An ultrasonic drive device includes the piezoelectric element according to the above-described aspect. With the ultrasonic drive device according to this aspect, drive performance and heat durability can be improved.
  • a sensing device includes the piezoelectric element according to the above-described aspect. With the sensing device configured according to this aspect, detection performance and heat durability can be improved.
  • a method for producing a lead-free piezoelectric ceramic composition includes: producing a molded product by mixing and molding a first crystal powder formed of an alkali niobate/tantalate perovskite oxide having piezoelectric characteristics with a second crystal powder formed of a compound that contains titanium (Ti); and producing a lead-free piezoelectric ceramic composition, in which a first crystal phase is formed by binding a plurality of crystal grains of the first crystal powder in a deposited state and a second crystal phase is formed by melting the second crystal powder to fill spaces between the plurality of crystal grains of the first crystal phase, by firing the molded product.
  • a lead-free piezoelectric ceramic composition of improved piezoelectric characteristics over the piezoelectric characteristics of other lead-free piezoelectric ceramic compositions that do not include the second crystal phase.
  • a method for producing a lead-free piezoelectric ceramic composition according to another aspect of the present invention includes: calcining a mixed powder of a first crystal powder and a second crystal powder at a first temperature, the first crystal powder being formed of an alkali niobate/tantalate perovskite oxide having piezoelectric characteristics and the second crystal powder being formed of a compound that contains titanium (Ti); producing a molded product by mixing and molding the mixed powder calcined at the first temperature; and producing a lead-free piezoelectric ceramic composition, in which a first crystal phase is formed by binding a plurality of crystal grains of the first crystal powder in a deposited state and a second crystal phase is formed by melting the second crystal powder to fill spaces between the plurality of crystal grains of the first crystal phase, by firing the molded product at a second temperature higher than the first temperature.
  • the aspects of the present invention are not limited to the aspects of the lead-free piezoelectric ceramic composition, the piezoelectric element, the ultrasonic processing machine, the ultrasonic drive device, the sensing device, and the lead-free piezoelectric ceramic composition producing method, and are also applicable to, for example, various types of devices that use lead-free piezoelectric ceramic compositions, and to various methods for producing such devices.
  • the present invention is in no way limited to the foregoing aspects, and can be implemented in a wide range of aspects within the gist of the present invention.
  • FIG. 1 is an explanatory view showing a structure of a typical lead-free piezoelectric ceramic composition
  • FIG. 2 is an explanatory view representing a piezoelectric element producing method
  • FIG. 3 is a perspective view showing a piezoelectric element of an embodiment of the present invention.
  • FIG. 4 is an exploded perspective view showing a sensing device of an embodiment of the present invention.
  • FIG. 5 is a longitudinal sectional view of an ultrasonic drive device of an embodiment of the present invention.
  • FIG. 6 is a perspective view showing an ultrasonic processing machine of an embodiment of the present invention.
  • FIG. 7 is an explanatory view representing the results of experiments for the effects of subphase content and component element on piezoelectric ceramic composition characteristics
  • FIG. 8 is a graph representing the result of an experiment for the effect of subphase content on the voltage constant of the piezoelectric ceramic composition
  • FIG. 9 is an explanatory view representing the results of experiments for the effect of subphase content and other variables on transition temperature
  • FIG. 10 is an explanatory view representing the results of experiments for the effect of the coefficient of the mother phase composition formula on the characteristics of the piezoelectric ceramic composition
  • FIG. 11 is a graph representing the result of an experiment for the effect of the coefficient of the mother phase composition formula on the piezoelectric constant of the piezoelectric ceramic composition
  • FIG. 12 is an explanatory view representing the results of experiments for the effect of additional metals on the characteristics of the piezoelectric ceramic composition
  • FIG. 13 is an explanatory view representing the results of experiments for the effect of the presence or absence of subphase on the insulation of the piezoelectric ceramic composition
  • FIG. 14 is an explanatory view representing the results of the qualitative analyses of the second crystal phase in the piezoelectric ceramic composition
  • FIG. 15 is an explanatory view representing the results of the qualitative analysis of the second crystal phase in the piezoelectric ceramic composition
  • FIG. 16 is an explanatory view representing the results of experiments for the effect of additional metals on the characteristics of the piezoelectric ceramic composition
  • FIG. 17 is an explanatory view representing the results of the thermal cycle evaluation test for the piezoelectric ceramic composition
  • FIG. 18 is an explanatory view representing the results of experiments for the effect of subphase content on the characteristics of the piezoelectric ceramic composition
  • FIG. 19 is a graph representing the result of an experiment for the effect of subphase content on the porosity of the piezoelectric ceramic composition
  • FIG. 20 is a graph representing the result of an experiment for the effect of subphase content on the voltage constant of the piezoelectric ceramic composition
  • FIG. 21 is a graph representing the result of an experiment for the effect of subphase content on the dielectric breakdown voltage of the piezoelectric ceramic composition
  • FIG. 22 is an explanatory view representing the effects of subphase content and producing method on the structure of the lead-free piezoelectric ceramic composition
  • FIG. 23 is an explanatory view showing distributions of trace elements in the piezoelectric ceramic composition
  • FIG. 24 is an explanatory view representing a piezoelectric element producing method
  • FIG. 25 is an explanatory view representing the results of experiments for the characteristics of the piezoelectric ceramic composition
  • FIG. 26 is an explanatory view representing the result of an experiment for the characteristics of the piezoelectric ceramic composition
  • FIG. 27 is an explanatory view representing the result of an experiment for the dynamic characteristics of a transducer.
  • FIG. 28 is an explanatory view representing the result of an experiment for the static characteristic of a transducer.
  • the piezoelectric ceramic composition as an embodiment of the present invention is a lead-free piezoelectric ceramic composition that mainly includes a first crystal phase formed of a compound having piezoelectric characteristics, and a second crystal phase formed of a compound that does not have piezoelectric characteristics.
  • the lead-free piezoelectric ceramic composition as an embodiment of the present invention typically includes the second crystal phase in a proportion of more than 0 mol % and less than 20 mol %, and the first crystal phase accounting for the reminder.
  • the first crystal phase will also be referred to as a “mother phase” or “KNN phase”
  • the second crystal phase as a “subphase” or “NTK phase”.
  • FIG. 1 is an explanatory view showing a structure of a typical lead-free piezoelectric ceramic composition.
  • the structure shown in FIG. 1 is of a sample prepared as a thin section of a lead-free piezoelectric ceramic composition after dimpling and ion milling, as observed under a transmission electron microscope (TEM-EDS).
  • TEM-EDS transmission electron microscope
  • the black portion indicates a first crystal phase (mother phase) 10
  • the white portion indicates a second crystal phase (subphase) 20 .
  • the first crystal phase 10 is preferably a crystal phase in which a plurality of crystal grains is bound to each other in a deposited state
  • the second crystal phase 20 is preferably a crystal phase that fills the spaces between the crystal grains of the first crystal phase 10 .
  • the second crystal phase 20 forming the three-dimensional mesh structure restrains the first crystal phase 10 and creates a distortion in the first crystal phase 10 , and thus improves the piezoelectric characteristics.
  • the second crystal phase 20 having a lower melting point than the first crystal phase 10 , assumes a liquid phase while the lead-free piezoelectric ceramic composition is being sintered, and fills the spaces in the first crystal phase 10 to suppress formation of pores, thereby improving sinterability and insulation.
  • the domain structure is segmented at the time of the polarization, and the piezoelectric characteristics improve.
  • the thermal behaviors of the first crystal phase 10 and the second crystal phase 20 are different, the temperature characteristics are more stabilized compared with using the first crystal phase 10 alone.
  • an alkali niobate/tantalate perovskite oxide is used as the compound forming the first crystal phase 10 .
  • alkali niobate/tantalate perovskite oxide is a collective term used to refer to two types of perovskite oxides, specifically an alkali niobate perovskite oxide and an alkali tantalate perovskite oxide.
  • the alkaline component of the alkali niobate/tantalate perovskite oxide forming the first crystal phase 10 contains at least alkali metals (such as K (potassium), Na (sodium), and Li (lithium)), and may contain alkali earth metals (such as Ca (calcium), Sr (strontium), and Ba (barium)).
  • alkali niobateltantalate perovskite oxide preferably represents those represented by the following composition formula.
  • the element E is at least one alkali earth metal selected from Ca (calcium), Sr (strontium), and Ba (barium).
  • the element D is at least one of Nb (niobium) and Ta (tantalum).
  • the alkali niobate/tantalate perovskite oxide is a perovskite oxide that may contain one or more alkali metals (K, Na, Li), and alkali earth metals (Ca, Sr, Ba) at the A site, and that contains at least one of Nb (niobium) and Ta (tantalum) at the B site.
  • coefficients a to f in the composition formula are selected in combinations that establish the perovskite structure, and that are preferred from the standpoint of the electrical characteristics or piezoelectric characteristics (particularly, piezoelectric constant d 33 ) of the lead-free piezoelectric ceramic composition.
  • the coefficients a and b of K (potassium) and Na (sodium) are typically 0 ⁇ a ⁇ 0.6, and 0 ⁇ b ⁇ 0.6.
  • the coefficient c of Li may be zero, and is preferably 0 ⁇ c ⁇ 0.2, further preferably 0 ⁇ c ⁇ 0.1.
  • the coefficient d of the element E (Ca, Sr, Ba) may be zero, and is preferably 0 ⁇ d ⁇ 0.1, further preferably 0 ⁇ d ⁇ 0.05.
  • the coefficient e for the A site as a whole may have any value, and is typically 0.9 ⁇ e ⁇ 1.1, preferably 0.97 ⁇ e ⁇ 1.08, and further preferably 1.00 ⁇ e ⁇ 1.08.
  • K, Na, and Li have a valency of +1
  • element E (Ca, Sr, Ba) has a valency of +2
  • element D (Nb, Ta) has a valency of +5
  • O oxygen
  • the coefficient f takes any value that allows the first crystal phase 10 to form the perovskite oxide, and typically has a value of approximately 3. From the electrical neutralization conditions of the composition, the coefficients a to f can be represented by the following equation (1). ( a+b+c+ 2 ⁇ d ) ⁇ e+ 5 ⁇ 2 ⁇ f (1)
  • a typical composition of the first crystal phase 10 is (K, Na, Li, Ca) 1.07 NbO 3.06 (coefficients a to d are omitted).
  • the first crystal phase 10 of the composition above contains K (potassium), Na (sodium), and Nb (niobium) as the main metallic components, and as such the material is also referred to as “KNN material”, and the first crystal phase 10 as “KNN phase”.
  • KNN material potassium (potassium), Na (sodium), and Nb (niobium) as the main metallic components
  • KNN material the material
  • a piezoelectric ceramic composition having excellent characteristics can be obtained at low cost upon selecting Ca (calcium) and Nb (niobium) as elements E and D, respectively.
  • a compound containing titanium (Ti) is used as the compound forming the second crystal phase 20 , and those represented by, for example, the following composition formula are preferably used.
  • the element A is at least one alkali metal (such as K (potassium), Rb (rubidium), and Cs (cesium)).
  • the element B is at least one of Nb (niobium) and Ta (tantalum).
  • the symbol x is any value.
  • the coefficient x satisfies 0 ⁇ x ⁇ 0.15. In this range of coefficient x, the second crystal phase 20 can have a stable structure, and a uniform crystal phase can be obtained.
  • Specific examples of the second crystal phase 20 in accordance with the foregoing composition formula include KTiNbO 5 , K 0.90 Ti 0.90 Nb 1.10 O 5 , K 0.85 Ti 0.85 Nb 1.15 O 5 , RbTiNbO 5 , Rb 0.90 Ti 0.90 Nb 1.10 O 5 , Rb 0.85 Ti 0.85 Nb 1.15 O 5 , CsTiNbO 5 , Cs 0.90 Ti 0.90 Nb 1.10 O 5 , KTiTaO 5 , and CsTiTaO 5 .
  • the coefficient x preferably satisfies 0 ⁇ x ⁇ 0.15 when element A is K (potassium) or Rb (rubidium), and 0 ⁇ x ⁇ 0.10 when element A is Cs (cesium).
  • a piezoelectric ceramic composition having excellent characteristics can be obtained at low cost upon selecting K (potassium) and Nb (niobium) as elements A and B, respectively.
  • the second crystal phase 20 does not have piezoelectric characteristics; however, the second crystal phase 20 can improve both sinterability and insulation by being used with the first crystal phase 10 . Further, the second crystal phase 20 is believed to have contribution in the effect of preventing the occurrence of a phase transition point between ⁇ 50° C. and +150° C.
  • the second crystal phase 20 is a laminar structure compound (or a laminar compound), and it is believed that, by being a laminar structure compound, the second crystal phase 20 improves the insulation of the piezoelectric ceramic composition and contributes to the effect of preventing the occurrence of a phase transition point. Note that the second crystal phase 20 as having a stable structure is disclosed in H. Rebbah et al., Journal of Solid State Chemistry, Vol. 31, p. 321-328, 1980, the entire disclosure of which is herein incorporated by reference.
  • the content of the second crystal phase 20 may be more than 0 mol % and less than 20 mol %, and is preferably from 2 mol % to 15 mol %, further preferably from 2 mol % to 10 mol %.
  • a composition that does not contain the second crystal phase 20 (a composition containing only the first crystal phase 10 ) tends to undergo abrupt characteristics fluctuations between ⁇ 50° C. and +150° C.
  • a content of the second crystal phase 20 in excess of 10 mol % has the risk of lowering the piezoelectric characteristics (particularly, piezoelectric constant d 33 ).
  • a typical composition of the second crystal phase 20 is K 0.85 Ti 0.85 Nb 1.15 O 5 .
  • the second crystal phase 20 of the composition above contains Nb (niobium), Ti (titanium), and K (potassium) as the main metallic components, and as such the material is also referred to as “NTK material”, and the second crystal phase 20 as “NTK phase”.
  • the second crystal phase 20 other than the crystal phase represented by A 1-x Ti 1-x B 1+x O 5 is a crystal phase represented by A 1 Ti 3 B 1 O 9 .
  • the coefficient 1 is intentionally recited in some cases to clearly distinguish the formula from the crystal phase represented by A 1-x Ti 1-x B 1+x O 5 .
  • the crystal phase represented by A 1-x Ti 1-x B 1+x O 5 is also referred to as “NTK1115 phase” or simply “1115 phase”, and the crystal phase represented by A 1 Ti 3 B 1 O 9 as “NTK1319 phase”, or simply “1319 phase”.
  • the element A is at least one alkali metal (such as K (potassium), Rb (rubidium), and Cs (cesium)), and the element B is at least one of Nb (niobium) and Ta (tantalum).
  • the second crystal phase 20 represented by A 1 Ti 3 B 1 O 9 does not have piezoelectric characteristics; however, the second crystal phase 20 of this composition also can improve both sinterability and insulation by being used with the first crystal phase 10 .
  • the second crystal phase 20 of the composition above is also believed to have contribution in the effect of preventing the occurrence of a phase transition point between ⁇ 50° C. and +150° C.
  • the content of the second crystal phase 20 represented by A 1 Ti 3 B 1 O 9 may be more than 0 mol % and less than 20 mol %, and is preferably from 2 mol % to 15 mol %, further preferably from 2 mol % to 10 mol %.
  • a composition that does not contain the second crystal phase 20 (a composition containing only the first crystal phase 10 ) tends to undergo abrupt characteristics fluctuations between ⁇ 50° C. to +150° C. Further, a content of the second crystal phase 20 in excess of 10 mol % has the risk of lowering the piezoelectric characteristics (particularly, piezoelectric constant d 33 ).
  • the crystal phase represented by A 1-x Ti 1-x B 1+x O 5 , and the crystal phase represented by A 1 Ti 3 B 1 O 9 are common in that both are compound oxides of element A (alkali metal), Ti (titanium), and element B (at least one of Nb and Ta).
  • Such compound oxides of element A, Ti (titanium), and element B are called “A-Ti—B—O compound oxides”.
  • an A-Ti—B—O compound oxide (element A is an alkali metal; element B is at least one of Nb and Ta; and the contents of element A, element B, and Ti are not zero) may be used as the second crystal phase 20 .
  • an A-Ti—B—O compound oxide that does not have piezoelectric characteristics itself, and that can improve both sinterability and insulation by being used with the first crystal phase 10 , and can prevent the occurrence of a phase transition point between ⁇ 50° C. and +150° C.
  • the lead-free piezoelectric ceramic composition as an embodiment of the present invention may contain at least one metal element selected from Cu (copper), Ni (nickel), Co (cobalt), Fe (iron), Mn (manganese), Cr (chromium), Zr (zirconium), Ag (silver), Zn (zinc), Sc (scandium), and Bi (bismuth). Adding these metal elements can improve the characteristics (particularly, piezoelectric constant d 33 ) of the lead-free piezoelectric ceramic composition.
  • the total content of the additional metals is preferably 5 mol % or less, further preferably 1 mol % or less. A total additional metal content in excess of 5 mol % has the risk of lowering the piezoelectric characteristics.
  • each additional metal is preferably added in less than 1 mol %.
  • a content of each additional metal exceeding 1 mol % has the risk of lowering the piezoelectric characteristics.
  • FIG. 2 is an explanatory view representing a piezoelectric element producing method.
  • the piezoelectric element produced by using the method of FIG. 2 is a device equipped with a piezoceramic formed of the lead-free piezoelectric ceramic composition.
  • the required raw material of the mother phase is selected from materials such as a K 2 CO 3 powder, a Na 2 CO 3 powder, a Li 2 CO 3 powder, a CaCO 3 powder, a SrCO 3 powder, a BaCO 3 powder, a Nb 2 O 5 powder, and a Ta 2 O 5 powder, and is weighed according to the values of the coefficients a to e in the mother phase composition formula. Then, ethanol is added to the raw material powders, and the whole is wet mixed with a ball mill for preferably at least 15 hours to obtain a slurry.
  • a mixed powder obtained by drying the slurry is calcined, for example, under an air atmosphere at 600 to 1,000° C. for 1 to 10 hours to produce a mother phase calcined product.
  • the required raw material of the subphase is selected from materials such as a K 2 CO 3 powder, a Rb 2 CO 3 powder, a Cs 2 CO 3 powder, a TiO 2 powder, a Nb 2 O 5 powder, and a Ta 2 O 5 powder, and is weighed according to the value of the coefficient x in the subphase composition formula. Then, ethanol is added to the raw material powders, and the whole is wet mixed with a ball mill for preferably at least 15 hours to obtain a slurry. In process T 140 , a mixed powder obtained by drying the slurry is calcined, for example, under the air atmosphere at 600 to 1,000° C. for 1 to 10 hours to produce a subphase calcined product.
  • the mother phase calcined product and the subphase calcined product are separately weighed, and pulverized and mixed with a ball mill after adding a dispersant, a binder, and ethanol to obtain a slurry.
  • the required material is selected from materials such as a CuO powder, an Fe 2 O 3 powder, a NiO powder, a Ag 2 O powder, a ZrO 2 powder, a ZnO powder, a MgO powder, a Sc 2 O 3 powder, a Bi 2 O 3 powder, a Cr 2 O 3 powder, a MnO 2 powder, and a CoO powder, weighed, and mixed into a slurry.
  • the slurry may be calcined again, and pulverized and mixed.
  • the additional metals added in process T 150 are metal oxides, and the content of each additional metal is preferably given in terms of the mol % of a simple substance metal.
  • the additional metals added to the first crystal phase (mother phase) and the second crystal phase (subphase) in process T 150 may be in the form of oxide EMO 3 (where element E is at least one of Ca, Sr, and Ba, and element M is the additional metal) that contains an alkali earth metal and the additional metal.
  • the element E (alkali earth metal element) contained as a third component in the oxide EMO3 is used as the element E in the first crystal phase of the piezoceramic after the firing.
  • process T 150 the slurry obtained from the mother phase calcined product and the subphase calcined product is dried, granulated, and uniaxially pressed to be molded into a desired shape (for example, disk shape or cylindrical shape), for example, under 20 MPa pressure. Subsequently, for example, the product is subjected to a CIP process (cold isostatic pressing) under 150 MPa pressure to obtain a CIP pressed body.
  • a CIP process cold isostatic pressing
  • the CIP pressed body obtained in process T 150 is held and fired, for example, under the air atmosphere at 900 to 1,300° C. for 1 to 10 hours to obtain a piezoceramic of the lead-free piezoelectric ceramic composition.
  • the firing may be performed under a reduction atmosphere or O 2 atmosphere.
  • the subphase NTK material has a lower melting point than the mother phase KNN material, and thus the plurality of crystal grains of KNN material in the mother phase melts in the maintained particle state during the firing performed in process T 160 , and the adjacent crystal grains bind to each other in the deposited state. Meanwhile, the subphase NTK material melts into a liquid phase, and flows into and fills the spaces formed between the crystal grains of the KNN material.
  • process T 170 the piezoceramic obtained in process T 160 is processed at the dimensional accuracy required of the piezoelectric element.
  • process T 180 electrodes are mounted on the piezoceramic, and a polarization process is performed in process T 190 .
  • the lead-free piezoelectric ceramic composition can be obtained that has improved piezoelectric characteristics over other lead-free piezoelectric ceramic compositions that do not have the second crystal phase.
  • the producing method described above is merely an example, and other processes and process conditions used for piezoelectric element production can be appropriately used.
  • the method that involves the mixing and firing of the mother phase calcined product and the subphase calcined product as in the producing method of FIG. 2 is also called a “two-phase control method”.
  • FIG. 24 is an explanatory view representing a piezoelectric element producing method.
  • the piezoelectric element produced by using the producing method of FIG. 24 is a device equipped with a piezoceramic of the lead-free piezoelectric ceramic composition.
  • the required raw material of the mother phase is selected from materials such as a K 2 CO 3 powder, a Na 2 CO 3 powder, a Li 2 CO 3 powder, a CaCO 3 powder, a SrCO 3 powder, a BaCO 3 powder, a Nb 2 O 5 powder, and a Ta 2 O 5 powder, and weighed according to the values of the coefficients a to e in the mother phase composition formula. Then, ethanol is added to the raw material powders, and the whole is wet mixed with a ball mill for preferably at least 15 hours to obtain a slurry.
  • a mixed powder obtained by drying the slurry is calcined, for example, under the air atmosphere at 600 to 1,000° C. for 1 to 10 hours to produce a mother phase calcined product.
  • the required raw material of the subphase is selected from materials such as a K 2 CO 3 powder, a Rb 2 CO 3 powder, a Cs 2 CO 3 powder, a TiO 2 powder, a Nb 2 O 5 powder, and a Ta 2 O 5 powder, and weighed according to the value of the coefficient x in the subphase composition formula. Then, ethanol is added to the raw material powders, and the whole is wet mixed with a ball mill for preferably at least 15 hours to obtain a slurry.
  • a mixed powder obtained by drying the slurry is calcined, for example, under the air atmosphere at 600 to 1,000° C. for 1 to 10 hours to obtain a calcined product and produce a subphase calcined product.
  • process T 252 the mother phase calcined product and the subphase calcined product are separately weighed, and pulverized and mixed with a ball mill after adding ethanol to obtain a slurry.
  • process T 254 a mixed powder obtained by drying the slurry is calcined under the air atmosphere at a first temperature (for example, 600 to 1,000° C.) for 1 to 10 hours to obtain a calcined product and produce a mixed calcined product.
  • the first temperature used for the calcining is lower than the temperature at which the powder derived from the subphase calcined product is sintered.
  • the mixed calcined product is weighed, and pulverized and mixed after adding a dispersant, a binder, and ethanol, to obtain a slurry.
  • the required material is selected from materials such as a CuO powder, an Fe 2 O 3 powder, a NiO powder, a Ag 2 O powder, a ZrO 2 powder, a ZnO powder, a MgO powder, a Sc 2 O 3 powder, a Bi 2 O 3 powder, a Cr 2 O 3 powder, a MnO 2 powder, and a CoO powder, weighed, and mixed into a slurry.
  • the additional metals added in process T 258 are metal oxides, and the content of each additional metal is preferably given in terms of the mol % of a simple substance metal.
  • the additional metals mixed with the first crystal phase (mother phase) and the second crystal phase (subphase) in process T 258 may be in the form of oxide EMO 3 (where the element E is at least one of Ca, Sr, and Ba, and the element M is the additional metal) that contains an alkali earth metal and the additional metal.
  • the element E (alkali earth metal element) contained as a third component in the oxide EMO 3 is used as the element E in the first crystal phase of the piezoceramic after the firing.
  • process T 258 the slurry obtained from the mother phase calcined product and the subphase calcined product is dried, granulated, and uniaxially pressed to be molded into a desired shape (for example, disk-shaped or cylindrical), for example, under 20 MPa pressure. Subsequently, for example, the product is subjected to a CIP process (cold isostatic pressing) under 150 MPa pressure to obtain a CIP pressed body.
  • a CIP process cold isostatic pressing
  • the CIP pressed body obtained in process T 258 is held and fired, for example, under the air atmosphere for 1 to 10 hours at a second temperature (for example, 900 to 1,300° C.) higher than the first temperature used for the calcining in process T 254 to obtain a piezoceramic of the lead-free piezoelectric ceramic composition.
  • the firing may be performed under a reduction atmosphere or O 2 atmosphere.
  • the subphase NTK material has a lower melting point than the mother phase KNN material, and thus the plurality of crystal grains of KNN material in the mother phase melts in the maintained particle state during the firing performed in process T 260 , and the adjacent crystal grains bind to each other in the deposited state. Meanwhile, the subphase NTK material melts into a liquid phase, and flows into and fills the spaces formed between the crystal grains of the KNN material.
  • process T 270 the piezoceramic obtained in process T 260 is processed at the dimensional accuracy required of the piezoelectric element.
  • process T 280 electrodes are mounted on the piezoceramic, and a polarization process is performed in process T 290 .
  • the lead-free piezoelectric ceramic composition can be obtained that has further improved piezoelectric characteristics over other lead-free piezoelectric ceramic compositions that do not have the second crystal phase.
  • the producing method described above is merely an example, and other processes and process conditions used for piezoelectric element production can be appropriately used.
  • the method that involves the mixing and firing of the mother phase calcined product and the subphase calcined product as in the producing method of FIG. 24 is also called a “two-phase control method”.
  • FIG. 3 is a perspective view showing a piezoelectric element 100 of an embodiment of the present invention.
  • the piezoelectric element 100 of FIG. 3 is produced by using the producing method of FIG. 2 , and includes a piezoceramic 110 , and a pair of electrodes 120 and 130 .
  • the piezoceramic 110 of the piezoelectric element 100 is formed from the lead-free piezoelectric ceramic composition, and has a disk shape in the example of FIG. 3 .
  • the electrodes 120 and 130 of the piezoelectric element 100 are mounted on the both sides of the piezoceramic 110 .
  • the electrodes 120 and 130 are disk-shaped as is the piezoceramic 110 , and are mounted on the both end surfaces of the piezoceramic 110 .
  • the piezoelectric element 100 can improve the piezoelectric characteristics. Note that the configuration of the piezoelectric element is not limited to the one shown in FIG. 3 , and the piezoelectric element can be implemented in a variety of configurations.
  • FIG. 4 is an exploded perspective view showing a sensing device 200 of an embodiment of the present invention.
  • the sensing device 200 is a detector that uses the piezoelectric element produced by using the producing method of FIG. 2 , and is a so-called non-resonant type knock sensor in the example of FIG. 4 .
  • the sensing device 200 includes a metal shell 210 , an insulating sleeve 220 , an insulating plate 230 , a piezoelectric element 240 , an insulating plate 250 , a characteristic adjusting weight 260 , a washer 270 , a nut 280 , and a housing 290 .
  • the metal shell 210 of the sensing device 200 is configured from a cylindrical tube 212 having formed therein a through hole 210 a , and a flange-like seating portion 214 extending out at one end portion of the tube 212 .
  • the circumference at the end portion of the tube 212 opposite from the seating portion 214 is engraved with screw threads 210 b .
  • the circumferential portions of the tube 212 and the seating portion 214 are engraved with grooves 210 c and 210 d , respectively, for improved contact with the housing 290 .
  • the metal shell 210 is an integral unit formed by using appropriate producing methods (such as casting, forging, and machining).
  • the surface of the metal shell 210 is plated (e.g., zinc chromate plating) to improve corrosion resistance.
  • the insulating sleeve 220 of the sensing device 200 is a hollow cylindrical member, and is formed of insulating material (e.g., plastic materials such as PET and PBT, and rubber materials).
  • the insulating plates 230 and 250 of the sensing device 200 are hollow disk-shaped members, and are formed of insulating material (e.g., plastic materials such as PET and PBT, and rubber materials).
  • the piezoelectric element 240 of the sensing device 200 is produced by using the producing method of FIG. 2 , and serves as a vibration detecting means for detecting vibration.
  • the piezoelectric element 240 is configured as a laminate of thin plate electrodes 242 and 246 , and a piezoceramic 244 disposed therebetween, and forms a hollow disk-shaped member as a whole.
  • the characteristic adjusting weight 260 of the sensing device 200 is a hollow disk-shaped member, and is formed of various metallic materials such as brass.
  • the washer 270 and the nut 280 of the sensing device 200 are formed of various metallic materials.
  • the insulating sleeve 220 is fitted to the tube 212 of the metal shell 210 .
  • the insulating plate 230 , the piezoelectric element 240 , the insulating plate 250 , and the characteristic adjusting weight 260 are fitted to the insulating sleeve 220 , in order.
  • the nut 280 is threadably mounted on the screw threads 210 b on the tube 212 of the metal shell 210 via the washer 270 .
  • the insulating plate 230 , the piezoelectric element 240 , the insulating plate 250 , the characteristic adjusting weight 260 , and the washer 270 are fixed by being held between the seating portion 214 of the metal shell 210 and the nut 280 .
  • the housing 290 formed of injection molded insulating material (various plastic materials such as PA) is provided for the metal shell 210 fixing its components, and the components fixed to the metal shell 210 are covered with the housing 290 .
  • the piezoelectric element 240 in the sensing device 200 is surrounded by the insulating sleeve 220 , the insulating plates 230 and 250 , and the housing 290 , and are electrically insulated from the metal shell 210 and the characteristic adjusting weight 260 .
  • Lead wires (not illustrated) leading out of the housing 290 are electrically connected to the thin plate electrodes 242 and 246 of the piezoelectric element 240 .
  • the sensing device 200 uses the piezoelectric element 240 of excellent piezoelectric characteristics, and can thus improve the detection performance and heat durability. It is therefore possible to suppress detection errors and inaccurate detection. It should be noted that the configuration of the sensing device is not limited to the one shown in FIG. 4 , and the sensing device can be implemented not only as a knock sensor but in a variety of other configurations, including ultrasonic sensors, and vibration sensors.
  • FIG. 5 is a longitudinal sectional view of an ultrasonic drive device 300 of an embodiment of the present invention.
  • the ultrasonic drive device 300 is a drive device that uses the piezoelectric element produced by using the producing method of FIG. 2 .
  • the ultrasonic drive device 300 is a so-called Langevin-type ultrasonic transducer.
  • the ultrasonic drive device 300 includes a piezoelectric element pair 310 , a front panel 320 , a backing panel 330 , and a center bolt 340 .
  • the piezoelectric element pair 310 of the ultrasonic drive device 300 is disposed between the front panel 320 and the backing panel 330 , and these are attached to each other in one piece with the center bolt 340 .
  • the piezoelectric element pair 310 includes a pair of hollow disk-shaped piezoelectric elements 312 and 314 , and a pair of electrode plates 313 and 315 .
  • the components of the piezoelectric element pair 310 are arranged in order from the piezoelectric element 312 , the electrode plate 313 , the piezoelectric element 314 , and to the electrode plate 315 , relative to the direction from the front panel 320 side toward the backing panel 330 .
  • the piezoelectric elements 312 and 314 are produced by using the producing method of FIG. 2 , and serve as a driving means for causing vibrations.
  • the front panel 320 and the backing panel 330 of the ultrasonic drive device 300 are formed of cylindrical metal blocks (for example, iron or aluminum).
  • the front panel 320 has a larger diameter than the piezoelectric element 312 , and the portion in contact with the piezoelectric element 312 is a conical portion 322 of decreasing diameters that match the diameter of the piezoelectric element 312 on the side of the piezoelectric element 312 .
  • the backing panel 330 has a larger diameter than the piezoelectric element 314 , and the portion in contact with the piezoelectric element 314 via the electrode plate 315 is a conical portion 332 of decreasing diameters that match the diameter of the piezoelectric element 314 on the side of the piezoelectric element 314 .
  • the diameters of the front panel 320 and the backing panel 330 are substantially the same.
  • the end portion of the front panel 320 opposite from the piezoelectric element pair 310 forms an ultrasonic radiation surface 328 where ultrasonic radiates.
  • the end portion of the backing panel 330 opposite from the piezoelectric element pair 310 side has a blind end hole 338 that extends along the axis line of the ultrasonic drive device 300 .
  • the total length along the axis line of the ultrasonic drive device 300 substantially coincides with the resonant length of the 3/2 wavelength of resonant frequency.
  • the ultrasonic drive device 300 uses the piezoelectric elements 312 and 314 of excellent piezoelectric characteristics, and can thus improve the drive performance and heat durability. It is therefore possible to produce ultrasonic at stable frequencies. It should be noted that the configuration of the ultrasonic drive device is not limited to the one shown in FIG. 5 , and the ultrasonic drive device can be implemented not only as an ultrasonic transducer but in a variety of other configurations, including ultrasonic actuators, and ultrasonic motors.
  • FIG. 6 is a perspective view showing an ultrasonic processing machine 400 of an embodiment of the present invention.
  • the ultrasonic processing machine 400 is a processing device that uses the piezoelectric element produced by using the producing method of FIG. 2 .
  • the ultrasonic processing machine 400 is a cutting tool for cutting a target object.
  • the ultrasonic processing machine 400 includes a base 410 , a piezoelectric element 420 , a grinding stone portion 430 , a spindle 440 , and a mounting jig 450 .
  • the base 410 of the ultrasonic processing machine 400 is a disk-shaped member, and has the grinding stone portion 430 formed around its circumference.
  • the center of the base 410 is fixed to the spindle 440 with the mounting jig 450 .
  • the piezoelectric element 420 of the ultrasonic processing machine 400 is produced by using the producing method of FIG. 2 .
  • the piezoelectric element 420 circular in shape, is embedded in the both surfaces of the base 410 , and serves as a driving means for producing vibration.
  • the drive direction of the piezoelectric element 420 is the radial direction from the center to the circumference of the base 410 .
  • the grinding stone portion 430 formed on the circumference of the base 410 is pressed against the target object while rotating the spindle 440 about the axis line under the vibration produced by the piezoelectric element 420 .
  • the ultrasonic processing machine 400 uses the piezoelectric element 420 of excellent piezoelectric characteristics, and can thus improve the process performance and heat durability. It should be noted that the configuration of the ultrasonic processing machine is not limited to the one shown in FIG. 6 , and the ultrasonic processing machine can be implemented not only as a cutting tool but in a variety of other configurations, including bonding devices (bonders), ultrasonic sealing devices, and ultrasonic cleaning machines.
  • the piezoelectric ceramic composition and the piezoelectric element of the embodiment of the present invention have a wide range of potential applications, including vibration detection, pressure detection, oscillation, and piezoelectric devices.
  • Examples include piezoelectric devices, such as sensors, transducers, actuators, and filters, high voltage generating devices, micro power sources, batteries, various drive devices, position control devices, vibration suppressing devices, fluid ejecting devices (such as coating ejection devices, and fuel ejection devices).
  • the piezoelectric ceramic composition and the piezoelectric element of the embodiment of the present invention are particularly preferable in applications where excellent heat durability is needed (for example, knock sensors, and combustion pressure sensors).
  • FIG. 7 is an explanatory view representing the results of experiments for the effects of subphase content and component element on piezoelectric ceramic composition characteristics.
  • the experiment results presented in FIG. 7 represent the characteristics of a plurality of sample compositions, including Examples of the present invention. These experiment results can be used to evaluate the effect of subphase content on the characteristics of the piezoelectric ceramic compositions. The results also can be used to evaluate the effects of the type of subphase component element B (Nb, Ta) and the type of main phase component element E (Ca, Sr, Ba) on the characteristics of the piezoelectric ceramic compositions.
  • Sample S 01 to S 04 in FIG. 7 were prepared as samples of a Comparative Example.
  • the samples S 01 and S 02 were configured from only the second crystal phase.
  • the samples S 01 and S 02 were prepared by weighing a K 2 CO 3 powder, a Nb 2 O 5 powder, and a TiO 2 powder to make the coefficient x in the composition formula of the second crystal phase as presented in FIG. 7 .
  • ethanol was added to the powders, and the whole was wet mixed with a ball mill for 15 hours to obtain a slurry.
  • a mixed powder obtained by drying the slurry was calcined under the air atmosphere at 600 to 1,000° C. for 1 to 10 hours to obtain a calcined product.
  • the calcined product was pulverized and mixed with a ball mill after adding a dispersant, a binder, and ethanol to obtain a slurry. Subsequently, the slurry was dried, granulated, and uniaxially pressed and molded into a disk shape (diameter 20 mm; thickness 2 mm) under 20 MPa pressure. Subsequently, the product was subjected to a CIP process under 150 MPa pressure, and the resulting CIP pressed body was held and fired under the air atmosphere at 900 to 1,300° C. for 1 to 10 hours.
  • the samples S 03 and S 04 were configured from only the first crystal phase.
  • the samples S 03 and S 04 were prepared by weighing a K 2 CO 3 powder, a Na 2 CO 3 powder, a Li 2 CO 3 powder, a Nb 2 O 5 powder to make the coefficients a, b, c, d, and e of the composition formula of the first crystal phase as presented in FIG. 7 .
  • ethanol was added to the powders, and the whole was wet mixed with a ball mill for 15 hours to obtain a slurry.
  • a mixed powder obtained by drying the slurry was calcined under the air atmosphere at 600 to 1,000° C. for 1 to 10 hours to obtain a calcined product.
  • the calcined product was pulverized and mixed with a ball mill after adding a dispersant, a binder, and ethanol to obtain a slurry. Subsequently, the slurry was dried, granulated, and uniaxially pressed and molded into a disk shape (diameter 20 mm; thickness 2 mm) under 20 MPa pressure. Subsequently, the product was subjected to a CIP process under 150 MPa pressure, and the resulting CIP pressed body was held and fired under the air atmosphere at 900 to 1,300° C. for 1 to 10 hours.
  • Samples S 05 to S 15 represent compositions that contain both the first crystal phase and the second crystal phase.
  • the samples S 05 to S 15 were prepared according to the processes T 110 to T 160 of FIG. 2 .
  • the samples after the molding in process T 150 had a disk shape (diameter 20 mm; thickness 2 mm)
  • the samples S 01 to S 15 were each subjected to the processes of processes T 170 to T 190 of FIG. 2 to prepare the piezoelectric element 100 ( FIG. 3 ).
  • the piezoelectric element 100 of each sample was then measured for electrical characteristics (relative permittivity ⁇ 33 T / ⁇ 0 ), and piezoelectric characteristics (piezoelectric constant d 33 and electromechanical coupling coefficient kr). The results are presented in FIG. 7 .
  • the samples S 01 and S 02 configured from only the second crystal phase did not have piezoelectric characteristics. These samples S 01 and S 02 had different values for the coefficient x in the composition formula of the second crystal phase, and there was no difference in the relative permittivity ⁇ 33 T / ⁇ 0 . It is thus believed that the coefficient x in the composition formula of the second crystal phase has only small effects on the electrical characteristics and piezoelectric characteristics of the piezoelectric ceramic composition even in piezoelectric ceramic compositions that contain both the first crystal phase and the second crystal phase. In this respect, the coefficient x may have any value that can provide a stable, uniform crystal phase as the second crystal phase.
  • the samples S 03 and S 04 configured from only the first crystal phase had piezoelectric characteristics. These samples S 03 and S 04 are common in that neither of them contains element E (Ca, Sr, Ba). The difference lies in Li, which is contained in the sample S 04 but not in the sample S 03 .
  • the element D of the first crystal phase is Nb (niobium).
  • the samples S 03 and S 04 do not differ greatly with regard to electrical characteristics (relative permittivity ⁇ 33 T / ⁇ 0 ) and piezoelectric characteristics (piezoelectric constant d 33 and electromechanical coupling coefficient kr). However, the sample S 04 containing Li is more preferable because it has a slightly larger piezoelectric constant d 33 than the sample S 03 containing no Li. Considering this, it is preferable that the first crystal phase contain Li even in piezoelectric ceramic compositions that contain both the first crystal phase and the second crystal phase.
  • the sample S 05 is a composition that contains 5 mol % of the second crystal phase with the first crystal phase.
  • the first crystal phase did not contain element E (Ca, Sr, Ba), and the coefficient x in the composition formula of the second crystal phase was zero.
  • the sample S 05 is equivalent to a combination of the samples S 01 and S 04 .
  • the sample S 05 had much greater values of relative permittivity ⁇ 33 T / ⁇ 0 and piezoelectric constant d 33 , and its characteristics were preferable as a piezoelectric ceramic composition.
  • the sample S 05 was also superior to the sample S 04 in terms of electromechanical coupling coefficient kr.
  • the samples S 06 to S 12 are compositions containing varying subphase contents of from 3 mol % to 20 mol %.
  • the composition of the first crystal phase was (K 0.421 Na 0.518 Li 0.022 Ca 0.039 ) 1.07 NbO 3.06 for the samples S 06 to S 12 .
  • the composition of the second crystal phase was K 0.85 Ti 0.85 B 1.15 O 5 for the samples S 06 to S 12 .
  • the samples S 06 to S 12 were more preferable because they had sufficiently larger values of relative permittivity ⁇ 33 T / ⁇ 0 than the sample S 04 of the Comparative Example. From the standpoint of relative permittivity, the subphase content preferably ranges from 3 to 10 mol %, further preferably 3 to 6 mol %.
  • the samples S 06 to S 11 were also more preferable for their sufficiently larger values of piezoelectric constant d 33 than that of the sample S 04 of the Comparative Example.
  • the sample S 12 with the subphase content of 20 mol % is less preferable than the sample S 04 of the Comparative Example for its smaller piezoelectric constant d 33 .
  • FIG. 8 is a graph representing the result of an experiment for the effect of subphase content on the voltage constant d 33 of the piezoelectric ceramic composition.
  • FIG. 8 represents changes in piezoelectric constant d 33 for the samples S 06 to S 12 .
  • the horizontal axis represents subphase content
  • the vertical axis represents piezoelectric constant d 33 .
  • the subphase content preferably ranges from 3 to 15 mol %, further preferably 3 to 10 mol %, most preferably 4 to 6 mol % from the standpoint of piezoelectric constant d 33 .
  • the electromechanical coupling coefficients kr ( FIG. 7 ) of the samples S 06 to S 11 are comparable to or better than that of the sample S 04 of the Comparative Example, and all are preferable.
  • the sample S 12 with a subphase content of 20 mol % is less preferable than that of the sample S 04 of the Comparative Example for its considerably smaller electromechanical coupling coefficient kr.
  • the subphase content preferably ranges from 3 to 10 mol %, further preferably 4 to 6 mol %.
  • the samples S 05 and S 08 are common in that the subphase content is 5 mol %. A significant difference, however, is that the first crystal phase of the sample S 05 does not contain element E (Ca, Sr, Ba) at all, whereas the first crystal phase of the sample S 08 contains Ca (calcium) as element E.
  • the samples S 05 and S 08 have different values of coefficient x in the composition formula of the second crystal phase. However, as discussed in conjunction with the samples S 01 and S 02 , the effect of the difference in the value of coefficient x on the characteristics of the piezoelectric ceramic composition is believed to be relatively small.
  • the sample S 08 containing Ca (calcium) in the first crystal phase is superior with respect to all of relative permittivity ⁇ 33 T / ⁇ 0 , piezoelectric constant d 33 , and electromechanical coupling coefficient kr. It is therefore preferable that the first crystal phase contain Ca as the component element E. Similarly, the same effect can be expected for other alkali earth elements (such as Sr and Ba) contained as component element E.
  • relative permittivity ⁇ 33 T / ⁇ 0 piezoelectric constant d 33
  • electromechanical coupling coefficient kr electromechanical coupling coefficient kr
  • a composition with a large relative permittivity ⁇ 33 T / ⁇ 0 is suited for capacitors.
  • a composition with a large piezoelectric constant d 33 is suited for actuators and sensors.
  • a composition with a large electromechanical coupling coefficient kr is suited for piezoelectric transformers and actuators. Whether to use which piezoelectric ceramic composition is suitably determined according to the characteristics required of each different application.
  • the samples S 13 and S 14 in FIG. 7 were prepared to mainly examine the effect of the element B (Nb, Ta) of the second crystal phase. These samples are not much different with regard to relative permittivity ⁇ 33 T / ⁇ 0 , piezoelectric constant d 33 , and electromechanical coupling coefficient kr. It can thus be understood that Nb and Ta are both preferable as the element B.
  • the sample S 14 has a composition similar to that of the sample S 08 . Namely, the compositions of these samples are essentially the same, the main difference being the amount Ca contained as the component element E of the first crystal phase, and accordingly the amounts of K and Na.
  • the sample S 14 containing more Ca is more preferable from the standpoint of relative permittivity ⁇ 33 T / ⁇ 0 .
  • the sample S 08 containing less Ca is more preferable from the standpoint of piezoelectric constant d 33 and electromechanical coupling coefficient kr.
  • the sample S 15 contains Ca and Sr in the same amounts (the same at %) as the component element E of the first crystal phase.
  • the composition is otherwise similar to that of the sample S 08 .
  • the sample S 15 is not as desirable as the sample S 08 in all of relative permittivity ⁇ 33 T / ⁇ 0 , piezoelectric constant d 33 , and electromechanical coupling coefficient kr.
  • the sample S 15 is more preferable than the sample S 04 of the Comparative Example for its sufficiently large relative permittivity ⁇ 33 T / ⁇ 0 and piezoelectric constant d 33 .
  • a preferable composition can be obtained regardless of whether the alkali earth metal Ca or Sr is used as the component element E of the first crystal phase. It is thus expected that use of Ba instead of Ca or Sr (or in addition to Ca and Sr) would also provide similar characteristics. Note, however, that a piezoelectric ceramic composition of excellent characteristics can be provided at low cost when Ca is used as the component element E.
  • FIG. 9 is an explanatory view representing the results of experiments for the effect of subphase content and other variables on transition temperature.
  • FIG. 9 presents the results for the samples S 01 to S 15 as in FIG. 7 , and represents Curie points, and the results of an evaluation test for the presence or absence of phase transition at room temperature.
  • the samples S 05 to S 15 have Curie points in a range of 300 to 350° C. Typically, the Curie point of the piezoelectric ceramic composition is sufficient when it is 300° C. or more. Therefore, samples S 05 to S 15 all have sufficiently high Curie points.
  • the Curie point is mainly determined according to the characteristics of the first crystal phase, and thus it is believed that the Curie point of the whole piezoelectric ceramic composition does not fluctuate greatly even in the presence of slight changes in the subphase composition or subphase content.
  • the samples S 05 to S 12 and the samples S 14 to S 15 using Nb as the component element B of the second crystal phase have higher Curie points than the sample S 13 that uses Ta. Thus, as far as the Curie point is concerned, it is more preferable to use Nb, rather than Ta, as the component element B of the second crystal phase.
  • the relative permittivity ⁇ 33 T / ⁇ 0 was measured while gradually varying the ambient temperature over a temperature range of ⁇ 50° C. to +150° C.
  • a piezoelectric ceramic composition that undergoes phase transition in a certain temperature range experiences abrupt changes in relative permittivity ⁇ 33 T / ⁇ 0 , and shows a distinct peak according to temperature changes in this temperature range.
  • no such distinct peak occurs in relative permittivity ⁇ 33 T / ⁇ 0 , and changes are more gradual in a piezoelectric ceramic composition that does not undergo phase transition in such a temperature range.
  • room temperature means a temperature range wider than the common room temperature (25° C.), as can be understood from the context above.
  • Phase transition at room temperature was observed in the samples S 03 and S 04 of the Comparative Example. On the other hand, phase transition at room temperature was not observed in any of the samples S 05 to S 15 . Phase transition at room temperature is not preferable, because it greatly changes the electrical characteristics and piezoelectric characteristics of the piezoelectric ceramic composition before and after the transition. From this standpoint, the samples S 05 to S 15 containing both the first crystal phase and the second crystal phase are more preferable than the samples S 03 and S 04 of the Comparative Example for the absence of phase transition at room temperature.
  • FIG. 10 is an explanatory view representing the results of experiments for the effect of coefficient e of the mother phase composition formula on the characteristics of the piezoelectric ceramic composition.
  • FIG. 10 also presents the characteristics of the sample S 04 as the Comparative Example.
  • Samples S 21 to S 27 have the same values of coefficients a to d in the coefficients a to f of the composition formula of the first crystal phase, but have different values of coefficient e (the number of alkaline elements at A site).
  • the alkali earth metal (element E in the composition formula) contained in the first crystal phase is Ca (calcium).
  • the subphase contents are all 5 mol % in the samples S 21 to S 27 .
  • the coefficient x in the composition formula of the second crystal phase is zero, whereas the coefficient x is 0.15 in other samples S 22 to S 27 .
  • differences in coefficient x have only a small effect on characteristics. Note that the sample S 25 is the same as the sample S 14 presented in FIG. 7 .
  • the samples S 21 to S 27 are more preferable than the sample S 04 of the Comparative Example for their sufficiently larger values of relative permittivity ⁇ 33 T / ⁇ 0 .
  • the value of coefficient e in the composition formula of the first crystal phase preferably ranges from 0.97 to 1.1, further preferably 1.0 to 1.1.
  • the samples S 21 to S 25 are more preferable than the sample S 04 of the Comparative Example for their larger piezoelectric constants d 33 .
  • the samples S 26 and S 27 having coefficients e greater than 1.08 are less preferable than the sample S 04 of the Comparative Example for their smaller piezoelectric constants d 33 .
  • FIG. 11 is a graph representing the result of an experiment for the effect of coefficient e of the mother phase composition formula on the piezoelectric constant d 33 of the piezoelectric ceramic composition.
  • FIG. 11 represents values of piezoelectric constant d 33 for the samples S 21 to S 27 .
  • the horizontal axis represents values of coefficient e in the composition formula of the first crystal phase.
  • the coefficient e represents the ratio of the sum of the number of atoms of the alkali metal element (K+Na+Li) and the alkali earth metal element (element E in the composition formula) to the number of Nb (niobium) atoms.
  • the value of coefficient e in the composition formula of the first crystal phase preferably ranges from 0.97 to 1.08, further preferably 1.00 to 1.07 from the standpoint of piezoelectric constant d 33 .
  • the samples S 26 and S 27 are less preferable than the sample S 04 of the Comparative Example for their smaller electromechanical coupling coefficients kr.
  • the value of coefficient e in the composition formula of the first crystal phase preferably ranges from 0.97 to 1.08, further preferably 1.00 to 1.07 from the standpoint of electromechanical coupling coefficient.
  • FIG. 12 is an explanatory view representing the results of experiments for the effect of additional metals on the characteristics of the piezoelectric ceramic composition.
  • FIG. 12 also presents the characteristics of the sample S 04 as the Comparative Example.
  • Sample S 31 also represents a Comparative Example configured from only the first crystal phase, and contains 1 mol % of the additional metal Cu.
  • the sample S 31 has a smaller relative permittivity ⁇ 33 T / ⁇ 0 than the sample S 04 , but the electromechanical coupling coefficient kr is greater than that of the sample S 04 .
  • Samples S 32 to S 43 are compositions that contain 5 mol % of the second crystal phase.
  • the coefficients a and b in the coefficients a to f in the composition formula of the first crystal phase differ for different samples, whereas the other coefficients c to f are essentially the same.
  • the sample S 32 is the same as the sample S 08 presented in FIG. 7 , and does not contain an additional metal.
  • a piezoelectric ceramic composition of sufficiently more desirable characteristics over the samples S 04 and S 31 of the Comparative Example can be obtained when at least one metal element selected from Cu (copper), Ni (nickel), Co (cobalt), Fe (iron), Mn (manganese), Zr (zirconium), Ag (silver), Zn (zinc), Sc (scandium), and Bi (bismuth) is contained as the additional metal.
  • the additional metal selected from Cu (copper), Ni (nickel), Co (cobalt), Fe (iron), Mn (manganese), Zr (zirconium), Ag (silver), Zn (zinc), Sc (scandium), and Bi (bismuth) is contained as the additional metal.
  • adding Cr (chromium) is also expected to provide the same characteristics as with the case of adding Mn (manganese).
  • the content of each additional metal is preferably less than 1 mol %.
  • the total additional metal content is preferably 5 mol % or less. Containing additional metals in excess of these ranges is not preferable, because it may lower mainly the relative permittivity ⁇ 33 T / ⁇ 0 and the piezoelectric constant d 33 .
  • FIG. 13 is an explanatory view representing the results of experiments for the effect of the presence or absence of subphase on the insulation of the piezoelectric ceramic composition.
  • FIG. 13 represents the measured values of allowable voltage for the samples S 03 , S 04 , and S 08 described with reference to FIG. 7 , and for the sample S 35 described with reference to FIG. 12 .
  • the term “allowable voltage” means the maximum voltage that can be applied to the piezoelectric element 100 of each sample without causing damage, such as cracking, in the piezoceramic 110 .
  • voltage was applied for 30 min in an 80° C. environment, and the presence or absence of damage such as cracking in the piezoceramic 110 was examined.
  • the allowable voltage can be regarded as an index of the insulation of the piezoelectric ceramic composition.
  • FIG. 14 is an explanatory view representing the results of the qualitative analyses of the second crystal phase in the piezoelectric ceramic composition.
  • the first four the samples S 06 , S 08 , S 10 , and S 12 represent the piezoelectric ceramic compositions of the same sample numbers presented in FIG. 7 .
  • the samples S 33 , S 35 , S 36 , S 40 , and S 42 represent the piezoelectric ceramic compositions of the same sample numbers presented in FIG. 12 .
  • these nine samples were analyzed by XRD analysis (X-ray diffraction method), and TEM-EDS analysis (energy dispersive X-ray analysis using a transmission electron microscope). Note that the subphase composition, which is typically confirmed by using an X-ray diffraction method, may be confirmed by using techniques such as TEM-EDS when the amounts added or generated are small.
  • the last two columns at the right end of FIG. 14 represent the results of the qualitative analyses, in which “1115” means the 1115 phase (KTiNbO 5 phase), and “1319” the 1319 phase (KTi 3 NbO 9 phase).
  • “1115” means the 1115 phase (KTiNbO 5 phase)
  • “1319” the 1319 phase (KTi 3 NbO 9 phase).
  • the subphase of the piezoelectric ceramic composition is configured from the 1115 phase or 1319 phase alone, or from the 1115 phase and the 1319 phase together. It can be understood that the subphase is more likely to form the 1319 phase in the presence of the additional metal.
  • FIG. 15 is an explanatory view representing the results of the qualitative analysis of the second crystal phase in the piezoelectric ceramic composition.
  • the qualitative analysis results presented in FIG. 15 are those of the piezoelectric ceramic compositions prepared by mixing the mother phase material with the subphase material prepared as the 1319 phase.
  • the subphase content is 3 mol % for sample S 51 , and is 5 mol % for the other samples S 52 to S 57 .
  • the samples S 51 and S 52 do not contain additional metals, whereas the other samples S 53 to S 57 contain additional metals such as Cu, Fe, Zn, and Mn.
  • the subphase material prepared as the 1319 phase in processes T 130 and T 140 of FIG.
  • the samples S 51 to S 57 had characteristic similar to the characteristics (see FIG. 12 ) of the samples S 35 and S 36 presented in FIG. 14 , and excelled in all of electrical characteristics (relative permittivity ⁇ 33 T / ⁇ 0 ) and piezoelectric characteristics (piezoelectric constant d 33 and electromechanical coupling coefficient kr) (not presented in the figure).
  • FIG. 16 is an explanatory view representing the results of experiments for the effect of additional metals on the characteristics of the piezoelectric ceramic composition.
  • FIG. 16 represents the results of the experiments conducted for samples S 61 to S 81 different from the samples S 32 to S 43 of FIG. 12 .
  • FIG. 16 also presents the characteristics of the samples S 04 and S 31 presented in FIG. 12 as a Comparative Example. Each sample was produced by using the second crystal phase prepared as the 1115 phase. Referring to FIG. 16 , the samples S 61 to S 80 all contained the second crystal phase in 5 mol %, and the sample S 81 did not contain the second crystal phase.
  • the samples S 80 and S 81 were defective, as the compositions were not sufficiently densified by the firing in process T 160 of FIG. 2 . This is believed to be due to the excessively large value of coefficient e, 1.12, for the whole A site in the sample S 80 . It should be noted, however, that the sample S 79 with the coefficient e of 1.09, and the sample S 78 with the coefficient e of 0.98 both excelled in electrical characteristics (relative permittivity ⁇ 33 T / ⁇ 0 ) and piezoelectric characteristics (piezoelectric constant d 33 and electromechanical coupling coefficient kr).
  • the results presented in FIG. 16 taken together, suggest that, with the additional metals, the coefficient e in the composition formula of the first crystal phase preferably ranges from 0.97 to 1.10, further preferably 1.00 to 1.09.
  • a piezoelectric ceramic composition of sufficiently more desirable characteristics over the samples S 04 and S 31 of the Comparative Example can be obtained when at least one of Cu (copper), Ni (nickel), Co (cobalt), Fe (iron), Mn (manganese), Zr (zirconium), Ag (silver), Zn (zinc), Sc (scandium), and Bi (bismuth) is contained as the additional metal.
  • Adding Cr (chromium) is also expected to provide the same characteristics as with the case of adding Mn (manganese).
  • FIG. 17 is an explanatory view representing the results of the thermal cycle evaluation test for the piezoelectric ceramic composition.
  • the thermal cycle evaluation test was conducted for the three samples S 04 , S 31 , S 32 of FIG. 9 , and for the eight samples S 61 to S 65 , and S 67 to S 69 of FIG. 17 .
  • each sample was placed in a thermostatic chamber, and the piezoelectric characteristics at room temperature were evaluated (the “Initial value” column under the heading “Electromechanical coupling coefficient kr” in FIG. 17 ).
  • a thermal cycle was repeated by increasing and decreasing the temperature at a rate of 2° C./min over ⁇ 50° C., 150° C., 20° C., 150° C., and 20° C. The samples were held for 1 hour at each temperature. After the thermal cycle, the piezoelectric characteristics were reevaluated at room temperature (the “After thermal cycle” column under the heading “Electromechanical coupling coefficient kr” in FIG. 17 ).
  • the samples S 04 and S 31 containing no second crystal phase had large drop rates of approximately 70% in the electromechanical coupling coefficient kr after the thermal cycle.
  • the drop rate of electromechanical coupling coefficient kr after the thermal cycle was sufficiently smaller, approximately 10% to approximately 26%, and was more desirable in the samples S 32 , S 61 to S 65 , and S 67 to S 69 that contained the second crystal phase.
  • the piezoelectric ceramic composition containing the second crystal phase does not undergo an abrupt characteristic drop after the thermal cycle, and is preferable for applications where excellent heat durability is required (including, for example, knock sensors, and combustion pressure sensors).
  • FIG. 18 is an explanatory view representing the results of experiments for the effect of subphase content on the characteristics of the piezoelectric ceramic composition.
  • FIG. 18 represents the experiment results for the sample S 68 of FIG. 16 , and for the seven samples S 90 to S 96 of different subphase contents from the sample S 68 .
  • Samples S 90 to S 96 were produced by using the same method used for the sample S 68 , except that the subphase material was mixed with the mother phase material in different proportions in process T 150 of FIG. 2 . In the experiments represented in FIG.
  • the samples were measured for porosity and dielectric breakdown voltage, in addition to electrical characteristics (relative permittivity ⁇ 33 T / ⁇ 0 ) and piezoelectric characteristics (piezoelectric constant d 33 and electromechanical coupling coefficient kr).
  • FIG. 19 is a graph representing the result of an experiment for the effect of subphase content on the porosity of the piezoelectric ceramic composition.
  • FIG. 19 represents porosity changes for the samples S 68 , and S 90 to S 96 .
  • the horizontal axis represents subphase content, and the vertical axis represents porosity.
  • the porosity was 1.0 volume % (Vol %) in the sample S 90 that contained 1 mol % of the subphase content.
  • the sample S 91 with the subphase content of 2 mol % had a smaller porosity of 0.5 volume %.
  • the porosity was even smaller, 0.0 volume %, in the samples that contained 4 to 20 mol % of the subphase content, showing that the pores were eliminated.
  • the presence of pores in the piezoelectric ceramic composition is believed to lower the sinterability during the production, and the insulation of the piezoelectric ceramic composition. It is therefore preferable from the standpoint of porosity that the subphase content range from 2 to 20 mol %, further preferably 4 to 20 mol %.
  • FIG. 20 is a graph representing the result of an experiment for the effect of subphase content on the voltage constant d 33 of the piezoelectric ceramic composition.
  • FIG. 20 represents changes in piezoelectric constant d 33 for the samples S 68 , and S 90 to S 96 .
  • the horizontal axis represents subphase content
  • the vertical axis represents piezoelectric constant d 33 .
  • the samples with the subphase contents of 1 to 20 mol % desirably had piezoelectric constants d 33 of more than 100 pC/N.
  • the subphase content is preferably 2 to 10 mol %, further preferably 4 to 6 mol %, most preferably 5 mol %.
  • FIG. 21 is a graph representing the result of an experiment for the effect of subphase content on the dielectric breakdown voltage of the piezoelectric ceramic composition.
  • FIG. 21 represents changes in dielectric breakdown voltage for the samples S 68 , and S 90 to S 96 .
  • the horizontal axis represents subphase content, and the vertical axis represents dielectric breakdown voltage.
  • the subphase content is preferably 1 to 15 mol %, further preferably 2 to 10 mol %, most preferably 4 to 6 mol % from the standpoint of dielectric breakdown voltage.
  • FIG. 22 is an explanatory view representing the effects of subphase content and producing method on the structure of the lead-free piezoelectric ceramic composition.
  • the sample structures shown in FIG. 22 ( a ) to ( b ) are thin sections as observed under a transmission electron microscope (TEM-EDS) after dimpling and ion milling the lead-free piezoelectric ceramic composition.
  • TEM-EDS transmission electron microscope
  • the black portion indicates the first crystal phase (mother phase, KNN phase)
  • the white portion indicates the second crystal phase (subphase, NTK phase).
  • FIG. 22 ( a ) shows a structure of the sample S 90 ( FIG. 18 ) having the subphase content of 1 mol %.
  • the sample S 90 was produced by using the two-phase control method ( FIG. 2 ), and had a piezoelectric constant d 33 of 100 pC/N.
  • the second crystal phase was finely dispersed in the first crystal phase in the structure with the 1 mol % subphase content, and no crystal grains were confirmed in the first crystal phase.
  • FIG. 22 ( b ) shows a structure of the sample S 68 ( FIGS. 17 and 18 ) having the subphase content of 5 mol %.
  • the sample S 68 was produced by using the two-phase control method ( FIG. 2 ), and had a piezoelectric constant d 33 of 250 pC/N.
  • a plurality of crystal grains was bound to each other in the deposited state in the first crystal phase in the structure with the 5 mol % subphase content, and the second crystal phase filled the spaces between the crystal grains in the first crystal phase.
  • FIG. 22 ( c ) shows a structure of the sample S 94 ( FIG. 18 ) having the subphase content of 10 mol %.
  • the sample S 94 was produced by using the two-phase control method ( FIG. 2 ), and had a piezoelectric constant d 33 of 120 pC/N.
  • a plurality of crystal grains was bound to each other in the deposited state in the first crystal phase in the structure with the 10 mol % subphase content, and the second crystal phase filled the spaces in the first crystal phase as in FIG. 22 ( b ) .
  • the crystal grain surfaces in the first crystal phase were smoother than in FIG. 22 ( b ) , and the crystal grains in the first crystal phase were partially surrounded by the second crystal phase.
  • FIG. 22 ( d ) shows a structure of a sample that had the subphase content of 5 mol % and was prepared by using a method different from that used for the sample S 68 shown in FIG. 22 ( b ) .
  • the mother phase raw material and the subphase raw material were mixed with each other without being calcined, and molded and fired to produce the lead-free piezoelectric ceramic composition.
  • Such a producing method is called a normal solid-phase method.
  • the sample shown in FIG. 22 ( d ) had a piezoelectric constant d 33 of 160 pC/N. As shown in FIG.
  • a plurality of crystal grains in the first crystal phase was surrounded by the second crystal phase as expected in structures formed by the normal solid-phase method, and the structure was different from that produced by using the two-phase control method ( FIG. 22 ( b ) ).
  • the lead-free piezoelectric ceramic composition structure be formed of mainly the first crystal phase in which a plurality of crystal grains is bound to each other in the deposited state, and the second crystal phase that fills the spaces between the crystal grains in the first crystal phase. Further, from the standpoint of obtaining a structure having excellent piezoelectric characteristics, the lead-free piezoelectric ceramic composition is preferably produced by using the two-phase control method, rather than the normal solid-phase method.
  • FIG. 23 is an explanatory view showing distributions of trace elements in the piezoelectric ceramic composition.
  • the images in FIG. 23 ( a ) to ( f ) represent distributions of each trace element of the sample S 68 ( FIGS. 17 and 18 ), shown as a sample thin section as observed under a transmission electron microscope (TEM-EDS) after dimpling and ion milling the lead-free piezoelectric ceramic composition.
  • FIG. 23 ( a ) to ( f ) represents distributions of the trace elements Ti (titanium), Cu (copper), Zr (zirconium), Fe (iron), Zn (zinc), and calcium (Ca).
  • TEM-EDS transmission electron microscope
  • FIG. 23 ( a ) to ( f ) brighter portions contain more trace element of interest, and darker portions hardly contain a trace element of interest.
  • the images shown in FIG. 23 ( a ) to ( f ) were obtained by taking the same portion of the sample S 68 .
  • the trace elements Ti, Cu, Fe, Zn are localized in the second crystal phase (subphase, NTK phase) 20 .
  • the trace elements Zr and Ca are localized in the first crystal phase (mother phase, KNN phase) 10 .
  • the trace elements localized in the first crystal phase 10 and the second crystal phase 20 are believed to have effects on the piezoelectric characteristics of the lead-free piezoelectric ceramic composition.
  • FIG. 25 is an explanatory view representing the results of experiments for the characteristics of the piezoelectric ceramic composition.
  • FIG. 25 represents the results of the experiments conducted for the sample S 04 and samples S 101 to S 114 .
  • the experiments were conducted with respect to the relative permittivity ⁇ 33 T / ⁇ 0 , the compliance S 33 E , the piezoelectric constant d 33 , and the electromechanical coupling coefficient kr of each sample, as shown in FIG. 25 .
  • the samples S 101 to S 114 in FIG. 25 contain Ca as the element E1 of the first crystal phase, Ba as the element E2 of the first crystal phase, and the 1115 phase as the second crystal phase.
  • the samples S 101 to S 114 in FIG. 24 contain additional metals, for which at least two metal elements are selected from Cu (copper), Co (cobalt), Fe (iron), Zr (zirconium), Zn (zinc), and Co.
  • the samples S 04 and S 101 were produced by using the first producing method of FIG. 2 after the firing of the mixture of the mother phase calcined product and the subphase calcined product, without calcining the mixture.
  • the samples S 102 to S 114 were produced by using the second producing method of FIG. 24 after calcining (process T 254 ) and firing the mixture of the mother phase calcined product and the subphase calcined product.
  • the piezoelectric ceramic compositions containing at least two of the metal elements Cu (copper), Co (cobalt), Fe (iron), Zr (zirconium), Zn (zinc), and Co (cobalt) as the additional metals can have more desirable characteristics than the sample S 04 of the Comparative Example.
  • FIG. 26 is an explanatory view representing the result of an experiment for the characteristics of the piezoelectric ceramic composition.
  • the evaluation experiment was conducted for each of the samples S 04 , S 101 , and S 104 by measuring the dissipation tan ⁇ , indicative of a dielectric loss, upon application of alternating voltage according to the European Standard BS EN 50324-3:2002.
  • the experiment result for each sample is plotted in FIG. 26 , in which the horizontal axis represents voltage, and the vertical axis represents dissipation tan ⁇ .
  • the dissipation tan ⁇ is smaller (namely, a smaller dielectric loss) in any voltage range in the sample S 104 produced with calcining (process T 254 ) than in the sample S 101 produced without calcining (process T 254 ). It can also be seen that the difference in dissipation tan ⁇ between the samples S 101 and 104 increases with voltage increase.
  • the piezoelectric ceramic composition produced with calcining is superior to the piezoelectric ceramic composition produced without calcining (process T 254 ) in terms of electric field characteristics, and is more useful particularly in transducer applications that involve application of an electric field for driving.
  • FIG. 27 is an explanatory view representing the result of an experiment for the dynamic characteristics of a transducer.
  • the evaluation experiment was conducted for a transducer produced from each of the sample S 04 , S 101 , and S 104 , and by measuring the temperature of the transducer being driven at an amplitude of 15 ⁇ m (micrometers), a vibration rate of 700 mm/s, and an input electric power of 10 W (watt).
  • the result of the experiment for each sample is plotted as shown in FIG. 27 , in which the horizontal axis represents drive time, and the vertical axis represents transducer temperature.
  • the transducer using the sample S 04 underwent an abrupt temperature increase after 400 seconds of drive time, and failed to sustain its operation.
  • the transducers using the samples S 101 and S 104 underwent a gradual temperature increase after the start of the driving, and stabilized after 600 seconds of drive time, making it possible to stably sustain the driving of the transducers.
  • the temperature increase in the transducer using the sample S 104 produced with calcining is smaller than that in the transducer using the sample S 101 produced without calcining (process T 254 ).
  • FIG. 28 is an explanatory view representing the result of an experiment for the static characteristic of a transducer.
  • the evaluation experiment was conducted for a transducer produced from each of the samples S 04 , S 101 , S 104 as in the evaluation experiment of FIG. 27 , and by measuring the mechanical quality coefficient Qm under varying transducer temperatures. Larger mechanical quality coefficients Qm mean smaller losses.
  • the experiment result for each sample is represented in FIG. 28 , in which the horizontal axis represents transducer temperature, and the vertical axis represents mechanical quality coefficient Qm.
  • the present invention is not limited to the embodiments, examples, and variations described above, and can be realized in various configurations, provided that such changes do not depart from the gist of the present invention.
  • the technical features in the embodiments, examples, and variations corresponding to the technical features in the configurations described in the Summary of the Invention section can be appropriately replaced or combined to solve some of or all of the foregoing problems, or to achieve some of or all of the foregoing effects.
  • such technical features may be appropriately deleted if not described as being essential in the description of the present invention.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Piezo-Electric Or Mechanical Vibrators, Or Delay Or Filter Circuits (AREA)
  • Grinding And Polishing Of Tertiary Curved Surfaces And Surfaces With Complex Shapes (AREA)
US14/232,146 2011-07-13 2012-07-04 Lead-free piezoelectric ceramic composition, method for producing same, piezoelectric element using lead-free piezoelectric ceramic composition, ultrasonic processing machine, ultrasonic drive device, and sensing device Active 2033-08-29 US9828296B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2011154430 2011-07-13
JP2011-154430 2011-07-13
PCT/JP2012/004329 WO2013008418A1 (ja) 2011-07-13 2012-07-04 無鉛圧電磁器組成物およびその製造方法、ならびにその組成物を用いた圧電素子、超音波加工機、超音波駆動デバイスおよびセンシングデバイス

Publications (2)

Publication Number Publication Date
US20140139070A1 US20140139070A1 (en) 2014-05-22
US9828296B2 true US9828296B2 (en) 2017-11-28

Family

ID=47505728

Family Applications (1)

Application Number Title Priority Date Filing Date
US14/232,146 Active 2033-08-29 US9828296B2 (en) 2011-07-13 2012-07-04 Lead-free piezoelectric ceramic composition, method for producing same, piezoelectric element using lead-free piezoelectric ceramic composition, ultrasonic processing machine, ultrasonic drive device, and sensing device

Country Status (10)

Country Link
US (1) US9828296B2 (ko)
EP (1) EP2733131B1 (ko)
JP (1) JP5840144B2 (ko)
KR (1) KR101603447B1 (ko)
CN (1) CN103649008B (ko)
IN (1) IN2014DN00272A (ko)
MY (1) MY166346A (ko)
SG (1) SG2014002224A (ko)
TW (1) TWI518051B (ko)
WO (1) WO2013008418A1 (ko)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10340441B2 (en) * 2014-04-11 2019-07-02 Ngk Spark Plug Co., Ltd. Lead-free piezoelectric ceramic composition, piezoelectric element using the same, and method of manufacturing lead-free piezoelectric ceramic composition
US11070286B1 (en) 2020-05-07 2021-07-20 Ciena Corporation Opportunistic network defragmentation and optimization
US20220197386A1 (en) * 2020-12-18 2022-06-23 Tdk Taiwan Corp. Tactile feedback mechanism
US11552858B2 (en) 2020-11-23 2023-01-10 Ciena Corporation Reinforcement learning for optical network re-grooming

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG11201508052QA (en) * 2013-03-29 2015-10-29 Ngk Spark Plug Co Unleaded piezoelectric ceramic composition, piezoelectric element using same, device, and method for manufacturing unleaded piezoelectric ceramic composition
JP6297820B2 (ja) * 2013-11-15 2018-03-20 日本特殊陶業株式会社 圧電磁器組成物、圧電素子、内燃機関用センサ、及び圧電磁器組成物の製造方法
JP6327914B2 (ja) 2014-04-11 2018-05-23 日本特殊陶業株式会社 無鉛圧電磁器組成物、それを用いた圧電素子、及び、無鉛圧電磁器組成物の製造方法
JP5823014B2 (ja) 2014-04-11 2015-11-25 日本特殊陶業株式会社 無鉛圧電磁器組成物、それを用いた圧電素子、及び、無鉛圧電磁器組成物の製造方法
CN104117479B (zh) * 2014-07-11 2016-03-23 寿光市飞田电子有限公司 一种超声换能器外壳及超声换能器
DE102014118000A1 (de) * 2014-12-05 2016-06-09 Epcos Ag Anordnung mit einem DMS Filter und steiler rechter Flanke
WO2016157092A1 (en) 2015-04-01 2016-10-06 Sabic Global Technologies B.V. Shape-controlled ceramic fillers for enhanced piezoelectric properties of structured composites
TWI628439B (zh) * 2016-12-28 2018-07-01 國立成功大學 加速規及其製造方法
JP6895845B2 (ja) * 2017-08-09 2021-06-30 日本特殊陶業株式会社 無鉛圧電磁器組成物、圧電素子および圧電素子利用装置
JP6914151B2 (ja) * 2017-09-12 2021-08-04 日本特殊陶業株式会社 無鉛圧電磁器組成物、及び圧電素子
JP7151531B2 (ja) * 2019-02-14 2022-10-12 Tdk株式会社 圧電組成物、圧電素子、圧電デバイス、圧電トランス、超音波モータ、超音波発生素子およびフィルタ素子
JP7391186B2 (ja) * 2020-03-30 2023-12-04 京セラ株式会社 圧電磁器組成物及び圧電アクチュエータ
CN112830517A (zh) * 2020-12-30 2021-05-25 太原理工大学 一种钛铌酸盐的制备方法
EP4322233A1 (en) * 2021-04-08 2024-02-14 Niterra Co., Ltd. Lead-free piezoelectric porcelain composition and piezoelectric element

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5607632A (en) * 1995-05-30 1997-03-04 Rockwell International Corporation Method of fabricating PLZT piezoelectric ceramics
JP2000313664A (ja) 1999-02-24 2000-11-14 Toyota Central Res & Dev Lab Inc アルカリ金属含有ニオブ酸化物系圧電材料組成物
JP2001240471A (ja) 2000-02-29 2001-09-04 Kyocera Corp 圧電磁器組成物および圧電共振子
US20030071240A1 (en) 2001-05-29 2003-04-17 Masahiko Kimura Piezoelectric ceramic composition, piezoelectric ceramic element, and method for manufacturing the piezoelectric ceramic composition
US20030178605A1 (en) 2002-03-20 2003-09-25 Tatsuhiko Nonoyama Piezoelectric ceramic composition, its production method, and piezoelectric device and dielectric device
JP2004002051A (ja) 2001-05-29 2004-01-08 Murata Mfg Co Ltd 圧電磁器組成物、圧電セラミック素子および圧電磁器組成物の製造方法
US20040214723A1 (en) * 2003-03-14 2004-10-28 Denso Corporation Crystal oriented ceramics and production method of same
US20060006360A1 (en) * 2004-06-17 2006-01-12 Denso Corporation Grain oriented ceramics and production method thereof
JP2008174424A (ja) 2007-01-19 2008-07-31 Nagoya Institute Of Technology 無鉛圧電磁器複合体及びこれを用いた圧電素子
US20080305944A1 (en) * 2007-04-09 2008-12-11 Yaiyo Yuden Co., Ltd. Dielectric ceramics and manufacturing method thereof, as well as multilayer ceramic capacitor
US20100219724A1 (en) * 2007-09-07 2010-09-02 Michael Schossmann Ceramic Material, Method for Producing the Same, and Electro-Ceramic Component Comprising the Ceramic Material
WO2011093021A1 (ja) 2010-01-29 2011-08-04 日本特殊陶業株式会社 無鉛圧電磁器組成物、それを用いた圧電素子、ノックセンサ、及び、無鉛圧電磁器組成物の製造方法

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5607632A (en) * 1995-05-30 1997-03-04 Rockwell International Corporation Method of fabricating PLZT piezoelectric ceramics
JP2000313664A (ja) 1999-02-24 2000-11-14 Toyota Central Res & Dev Lab Inc アルカリ金属含有ニオブ酸化物系圧電材料組成物
US6387295B1 (en) 1999-02-24 2002-05-14 Kabushiki Kaisha Toyota Chuo Kenkyusho Alkali metal-containing niobate-based piezoelectric material composition and a method for producing the same
JP2001240471A (ja) 2000-02-29 2001-09-04 Kyocera Corp 圧電磁器組成物および圧電共振子
US20030071240A1 (en) 2001-05-29 2003-04-17 Masahiko Kimura Piezoelectric ceramic composition, piezoelectric ceramic element, and method for manufacturing the piezoelectric ceramic composition
JP2004002051A (ja) 2001-05-29 2004-01-08 Murata Mfg Co Ltd 圧電磁器組成物、圧電セラミック素子および圧電磁器組成物の製造方法
US20030178605A1 (en) 2002-03-20 2003-09-25 Tatsuhiko Nonoyama Piezoelectric ceramic composition, its production method, and piezoelectric device and dielectric device
JP2003342069A (ja) 2002-03-20 2003-12-03 Toyota Central Res & Dev Lab Inc 圧電磁器組成物及びその製造方法並びに圧電素子及び誘電素子
US20040214723A1 (en) * 2003-03-14 2004-10-28 Denso Corporation Crystal oriented ceramics and production method of same
US20060006360A1 (en) * 2004-06-17 2006-01-12 Denso Corporation Grain oriented ceramics and production method thereof
JP2008174424A (ja) 2007-01-19 2008-07-31 Nagoya Institute Of Technology 無鉛圧電磁器複合体及びこれを用いた圧電素子
US20080305944A1 (en) * 2007-04-09 2008-12-11 Yaiyo Yuden Co., Ltd. Dielectric ceramics and manufacturing method thereof, as well as multilayer ceramic capacitor
US20100219724A1 (en) * 2007-09-07 2010-09-02 Michael Schossmann Ceramic Material, Method for Producing the Same, and Electro-Ceramic Component Comprising the Ceramic Material
WO2011093021A1 (ja) 2010-01-29 2011-08-04 日本特殊陶業株式会社 無鉛圧電磁器組成物、それを用いた圧電素子、ノックセンサ、及び、無鉛圧電磁器組成物の製造方法
US20120146462A1 (en) 2010-01-29 2012-06-14 Ngk Spark Plug Co., Ltd. Lead-free piezoelectric ceramic composition, piezoelectric element comprising same, knock sensor, and process for production of lead-free piezoelectric ceramic composition
EP2530060A1 (en) 2010-01-29 2012-12-05 NGK Sparkplug Co., Ltd. Lead-free piezoelectric ceramic composition, piezoelectric element comprising same, knock sensor, and process for production of lead-free piezoelectric ceramic composition

Non-Patent Citations (10)

* Cited by examiner, † Cited by third party
Title
Ahn, et al., "Structural Variation and Piezoelectric Properties of 0.95 (Na0.5K0.5)NbO3-0.05BaTiO3 Ceramics", Sensors and Actuators, Nov. 22, 2006, vol. 136, Issue 1, pp. 255-260.
Darko Makovec et al.; "TiO2 as a sintering additive for KNbO3 ceramics"; Ceramics International; ScienceDirect; vol. 34; No. 1; 2008; pp. 89-94; XP022318852.
Hwi-Yeol Park et al.; "Microstructure and piezoelectric properties of lead-free (1-x)(Na0.5K0.5)NbO3-xCaTiO3 ceramics"; Journal of Applied Physics; American Institute of Physics; vol. 102; No. 12; Dec. 17, 2007; 6 pages total; XP012105224.
International Search Report (PCT/ISA/210) issued in International Application No. PCT/JP2012/004329; Sep. 18, 2012.
MAKOVEC, D. PRIBOSIC, I. DROFENIK, M.: "TiO"2 as a sintering additive for KNbO"3 ceramics", CERAMICS INTERNATIONAL., ELSEVIER, AMSTERDAM., NL, vol. 34, no. 1, 29 October 2007 (2007-10-29), NL, pages 89 - 94, XP022318852, ISSN: 0272-8842, DOI: 10.1016/j.ceramint.2006.08.008
Office Action dated Apr. 15, 2014, issued by the Japanese Patent Office in counterpart Japanese Application No. 2012-549192.
PARK HWI-YEOL; CHO KYUNG-HOON; PAIK DONG-SOO; NAHM SAHN; LEE HYEUNG-GYU; KIM DUK-HEE: "Microstructure and piezoelectric properties of lead-free (1−x)(Na0.5K0.5)NbO3-xCaTiO3 ceramics", JOURNAL OF APPLIED PHYSICS, AMERICAN INSTITUTE OF PHYSICS, US, vol. 102, no. 12, 17 December 2007 (2007-12-17), US, pages 124101 - 124101-5, XP012105224, ISSN: 0021-8979, DOI: 10.1063/1.2822334
Search Report dated Jan. 26, 2015 issued by the European Patent Office in counterpart European Patent Application No. 12811521.9.
Seo, et al.; "Effect of CuO on the Sintering and Piezoelectric Properties of 0.95 (Na0.5K0.5)NbO3-0.5SrTiO3 Lead-Free Piezoelectric Ceramics"; J. Am. Chem; vol. 91 No. 12; 2008; pp. 3955-3960.
Written Opinion (PCT/ISA/237) issued in International Application No. PCT/JP2012/004329; Sep. 18, 2012.

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10340441B2 (en) * 2014-04-11 2019-07-02 Ngk Spark Plug Co., Ltd. Lead-free piezoelectric ceramic composition, piezoelectric element using the same, and method of manufacturing lead-free piezoelectric ceramic composition
US11070286B1 (en) 2020-05-07 2021-07-20 Ciena Corporation Opportunistic network defragmentation and optimization
US11575431B2 (en) 2020-05-07 2023-02-07 Ciena Corporation Opportunistic network defragmentation and optimization
US11552858B2 (en) 2020-11-23 2023-01-10 Ciena Corporation Reinforcement learning for optical network re-grooming
US20220197386A1 (en) * 2020-12-18 2022-06-23 Tdk Taiwan Corp. Tactile feedback mechanism
US11835683B2 (en) * 2020-12-18 2023-12-05 Tdk Taiwan Corp. Tactile feedback mechanism

Also Published As

Publication number Publication date
EP2733131A1 (en) 2014-05-21
KR20140021068A (ko) 2014-02-19
US20140139070A1 (en) 2014-05-22
JPWO2013008418A1 (ja) 2015-02-23
CN103649008B (zh) 2016-03-02
MY166346A (en) 2018-06-25
WO2013008418A1 (ja) 2013-01-17
SG2014002224A (en) 2014-11-27
TW201329017A (zh) 2013-07-16
CN103649008A (zh) 2014-03-19
EP2733131A4 (en) 2015-02-25
IN2014DN00272A (ko) 2015-06-05
JP5840144B2 (ja) 2016-01-06
EP2733131B1 (en) 2020-10-28
KR101603447B1 (ko) 2016-03-14
TWI518051B (zh) 2016-01-21

Similar Documents

Publication Publication Date Title
US9828296B2 (en) Lead-free piezoelectric ceramic composition, method for producing same, piezoelectric element using lead-free piezoelectric ceramic composition, ultrasonic processing machine, ultrasonic drive device, and sensing device
US9006959B2 (en) Lead-free piezoelectric ceramic composition, piezoelectric element comprising same, knock sensor, and process for production of lead-free piezoelectric ceramic composition
US9938197B2 (en) Unleaded piezoelectric ceramic composition, piezoelectric element using same, device, and method for manufacturing unleaded piezoelectric ceramic composition
US9306149B2 (en) Piezoelectric material, piezoelectric element, liquid discharge head, ultrasonic motor, and dust removing device
US9842985B2 (en) Manufacturing method for piezoelectric ceramics
KR20150106971A (ko) 압전 재료
CN104891987A (zh) 陶瓷粉末、压电陶瓷、压电元件和电子设备
JP6357180B2 (ja) 磁器組成物、圧電素子、振動子、および、圧電素子の製造方法

Legal Events

Date Code Title Description
AS Assignment

Owner name: NGK SPARK PLUG CO., LTD., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:YAMAZAKI, MASATO;MATSUOKA, TAKAYUKI;KITAMURA, KAZUAKI;AND OTHERS;REEL/FRAME:031942/0993

Effective date: 20131225

STCF Information on status: patent grant

Free format text: PATENTED CASE

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1551); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 4

AS Assignment

Owner name: NITERRA CO., LTD., JAPAN

Free format text: CHANGE OF NAME;ASSIGNOR:NGK SPARK PLUG CO., LTD.;REEL/FRAME:064842/0215

Effective date: 20230630